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Title: Revisiting the Solution Structure of Ceric Ammonium Nitrate

Abstract

Ceric ammonium nitrate (CAN) is a single-electron-transfer reagent with unparalleled utility in organic synthesis, and has emerged as a vital feedstock in diverse chemical industries. Most applications use CAN in solution where it is assigned a monomeric [Ce-IV(NO3)(6)](2-) structure; an assumption traced to half-century old studies. Using synchrotron X-rays and Raman spectroscopy we challenge this tradition, converging instead on an oxo-bridged dinuclear complex, even in strong nitric acid. Thus, one equivalent of CAN is recast as a two-electron-transfer reagent and a redox-activated superbase, raising questions regarding the origins of its reactivity with organic molecules and giving new fundamental insight into the stability of polynuclear complexes of tetravalent ions.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science - Office of Basic Energy Sciences - Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1392400
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Volume: 54; Journal Issue: 26; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
ceric ammonium nitrate

Citation Formats

Demars, Thomas J., Bera, Mrinal K., Seifert, Soenke, Antonio, Mark R., and Ellis, Ross J. Revisiting the Solution Structure of Ceric Ammonium Nitrate. United States: N. p., 2015. Web. doi:10.1002/anie.201502336.
Demars, Thomas J., Bera, Mrinal K., Seifert, Soenke, Antonio, Mark R., & Ellis, Ross J. Revisiting the Solution Structure of Ceric Ammonium Nitrate. United States. doi:10.1002/anie.201502336.
Demars, Thomas J., Bera, Mrinal K., Seifert, Soenke, Antonio, Mark R., and Ellis, Ross J. Thu . "Revisiting the Solution Structure of Ceric Ammonium Nitrate". United States. doi:10.1002/anie.201502336.
@article{osti_1392400,
title = {Revisiting the Solution Structure of Ceric Ammonium Nitrate},
author = {Demars, Thomas J. and Bera, Mrinal K. and Seifert, Soenke and Antonio, Mark R. and Ellis, Ross J.},
abstractNote = {Ceric ammonium nitrate (CAN) is a single-electron-transfer reagent with unparalleled utility in organic synthesis, and has emerged as a vital feedstock in diverse chemical industries. Most applications use CAN in solution where it is assigned a monomeric [Ce-IV(NO3)(6)](2-) structure; an assumption traced to half-century old studies. Using synchrotron X-rays and Raman spectroscopy we challenge this tradition, converging instead on an oxo-bridged dinuclear complex, even in strong nitric acid. Thus, one equivalent of CAN is recast as a two-electron-transfer reagent and a redox-activated superbase, raising questions regarding the origins of its reactivity with organic molecules and giving new fundamental insight into the stability of polynuclear complexes of tetravalent ions.},
doi = {10.1002/anie.201502336},
journal = {Angewandte Chemie (International Edition)},
issn = {1433-7851},
number = 26,
volume = 54,
place = {United States},
year = {2015},
month = {4}
}

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